Unsaturated monomers, particularly olefin monomers, are polymerized in a variety of polymerization processes using a wide variety of monomer feeds to make a polymeric product. The polymerization reaction can be carried out using a wide variety of reactors, catalysts, and a wide variety of monomer feeds. Often, liquids, diluents or solvents are used in these polymerization reaction processes for various reasons such as to increase the efficiency of the polymerization reaction and recovery of polymer product. Polymer production at commercial scale typically results in the production of a polymer product having significant amounts of dissolved (or solubilized) hydrocarbon material such as unreacted monomer, as well as various levels of liquids, solvents, diluents, catalysts and other by-products and/or non-reactive components. The typical commercial polymerization processes used for olefin polymerization include gas phase, slurry phase, solution phase, and bulk phase. Gas phase polymerizations are those where the monomers are present, typically with a condensing fluid such as pentane, as a fluidizing gas and are contacted with a catalyst system, typically supported on silica, to form solid particles of polymer which are drawn out. These particles must then typically be treated or otherwise processed to remove unreacted monomers, condensing liquids, etc. Similarly, slurry phase polymerizations also tend to take place in the presence of a diluent. In slurry phase polymerizations, the catalyst may or may not be soluble in the diluent (and may or may not be supported), but the monomer typically is soluble in the diluent. As the monomer contacts the catalyst system polymer forms and separates out into another phase. Often it is said that the polymer precipitates out of the diluent. The polymer/diluent combination (also called the “slurry”) is then withdrawn from the reactor and steps are taken to separate the polymer from the residual monomers, diluents, etc. Similarly in bulk phase polymerizations, an excess of monomer to be polymerized is used as the diluent. Thus when the polymer forms and precipitates, there is often a fair amount of unreacted monomer solubilized in the polymer. As a consequence, when these polymer/monomer combinations exit the reactor, they too often need to be treated or processes to remove unreacted monomers, diluents, etc. Finally, in solution phase processes, unlike gas and slurry phase processes, the polymer is soluble in the reaction medium. Thus, when polymer is drawn out of a solution phase reactor, it is often subjected to several complicated treatments or processes to remove the solvent, unreacted monomers, and the like. With respect to solution phase processes in particular, the polymerization reaction mixture containing the polymer, solvent, and unreacted components typically passes from the polymerization reactor to a finishing section in which polymer, solvent and unreacted monomer are separated. In the course of finishing, solvent and unreacted monomer are progressively removed from the polymerization mixture until the polymer can be formed into a solid pellet or bale. The separated solvent and monomer are then typically recycled to the polymerization reactor.
Separation and recovery of the polymer product from such a mixture of components (e.g. unreacted monomer, as well as various levels of liquids, solvents, diluents, catalysts and other by-products and/or non-reactive components) typically involves passing the polymer product withdrawn from the polymerization reactor into purge bins, with nitrogen typically introduced into the purge bin to remove the undesirable materials from the polymer product. Conventionally, the nitrogen and undesirable material are vented or sent to a flare system as a waste stream. Other methods to remove these components include passing the material through sequential pressure vessels at progressively lower pressures. The lower pressure causes the unreacted monomers, solvents, diluents, and the like to desorb from the polymer as a mixed gas stream, which can be drawn off from the vessel and typically recycled.
Separation of solvents and unreacted monomer from the polymer is an important factor in any commercial polymerization process. For example, devolatilizing the solvent from the solution by steam stripping can be very energy-intensive because the solvent can be as much as 95 weight % of the solution. In certain solution polymerization processes, such as the production of ethylene/propylene copolymers, the cost of this separation could be up to 10% of the final product cost. Hence, improvements in the polymer recovery process could lead to substantial savings in the total product cost. Forcing a single-phase polymer solution to separate into two liquid equilibrium phases offers an alternative to steam stripping. A miscible polymer solution will separate into a polymer-rich phase and a polymer lean (solvent-rich) phase if a combination of temperature and/or pressure change results in the system crossing the upper or lower critical solution boundary region as shown on the isopleth (phase transition diagram.). The phase separation is controlled by the chemical nature of the components, their molecular sizes (especially the molecular weight of the polymer), and the critical temperature and critical pressure of the solvent mixture. The phase separation is encouraged by higher temperature and/or lower pressure in some systems and by higher pressure in others. Appropriate selection of polymerization solvent, monomer conversion, especially of the volatile monomers, temperatures, and pressures is required to induce phase separation. Some articles explaining the general principles are: “A low-energy Solvent Separation Method,” by T. G. Gutowski et al, Polymer Engineering; “Solvents” by C. A. Irani et al. in Journal of Applied Polymer Science Vol 31, 1879-1899 (1986); “Separating Polymer Solutions with Supercritical Fluids,” by Mark A. McHugh et al in Macromolecules 1985, 18, 674-680; “Critical Dynamics and Phase Separation Kinetics . . . ,” by Hajime Tanaka in Journal of Chemical Physics 100 (7) Apr. 1, 1994 p 5323-5337; “Short Chain Branching Effect on the Cloud Point Pressures of Ethylene Copolymers etc.,” by S. J. Han et al. in Macromolecules 1998, 31, 2533-2538.
For most solution processes, there is significant difference between the reaction conditions (temperature and pressure) and the critical conditions required for phase separation. Therefore, it is often necessary to heat the reactor effluent to the critical temperature or above to achieve phase separation. This extra step involves additional equipment, and more energy consumption as well as operational complexity, and risks polymer degradation a the higher temperatures.
Thus it is desirable to provide a more efficient polymer recovery system. This invention provides such improved polymer recovery method by, among other things, using fluorocarbon in the recovery processes.
U.S. Pat. No. 5,769,927 (Gottschlich et al.) discloses a process for treating material that is to be vented or purged from a polymer manufacturing operation using a three step separation technique. The technique includes condensation, flash evaporation and membrane separation to remove components such as ethylene, propylene and nitrogen. U.S. Pat. No. 6,271,319 (Baker et al.) discloses a polypropylene manufacturing process that includes using a gas separation membrane to separate propylene from propane in a reactor vent stream. The separated propylene is circulated back to the polymerization reactor as feed.
Fluorinated hydrocarbons have been previously used in polymerization processes including:
U.S. Pat. No. 3,470,143 discloses a process to produce a boiling-xylene soluble polymer in a slurry using certain fluorinated organic carbon compounds.
U.S. Pat. No. 5,990,251 discloses a gas phase process using a Ziegler-Natta catalyst system modified with a halogenated hydrocarbon, such as chloroform.
EP 0 459 320 A2 discloses polymerization in polar aprotic solvents, such as halogenated hydrocarbons.
U.S. Pat. No. 5,780,565 discloses dispersion polymerizations of polar monomers under super-atmospheric conditions such that the fluid is a liquid or supercritical fluid, the fluid being carbon dioxide, a hydrofluorocarbon, a perfluorocarbon or a mixture thereof.
U.S. Pat. No. 5,624,878 discloses the polymerization using “constrained geometry metal complexes” of titanium and zirconium.
U.S. Pat. No. 2,534,698, U.S. Pat. No. 2,644,809 and U.S. Pat. No. 2,548,415 disclose preparation of butyl rubber type elastomers in fluorinated solvents.
U.S. Pat. No. 6,534,613 discloses use of hydrofluorocarbons as catalyst modifiers.
U.S. Pat. No. 4,950,724 disclose the polymerization of vinyl aromatic monomers in suspension polymerization using fluorinated aliphatic organic compounds.
WO 02/34794 discloses free radical polymerizations in certain hydrofluorocarbons.
WO 02/04120 discloses a fluorous bi-phasic systems.
WO 02/059161 discloses polymerization of isobutylene using fluorinated co-initiators.
EP 1 323 746 shows loading of biscyclopentadienyl catalyst onto a silica support in perfluorooctane and thereafter the prepolymerization of ethylene at room temperature.
U.S. Pat. No. 3,056,771 discloses polymerization of ethylene using TiCl4/(Et)3Al in a mixture of heptane and perfluoromethylcyclohexane, presumably at room temperature, further a mixture of 30% perfluoromethylcyclohexane in heptane was used to cause the polymer in the slurry to float.
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